1. Field of the Invention
The present invention is directed to a cordierite ceramic honeycomb article for use as a catalyst carrier, and methods of manufacturing same. More particularly, the invention is directed to a cordierite honeycomb article having good washcoatability as a virtue of a relatively high porosity, and good thermal shock resistance by virtue of a relatively low coefficient of thermal expansion (CTE).
2. Technical Background
The exhaust gases emitted by internal combustion systems utilizing hydrocarbon fuels, such as hydrocarbon gases, gasoline or diesel fuel, can cause serious pollution of the atmosphere. Among the many pollutants in these exhaust gases are hydrocarbons and oxygen-containing compounds, the latter including nitrogen oxides (NOx) and carbon monoxide (CO). The automotive industry has for many years attempted to reduce the quantities of pollutants from automobile engine systems, the first automobiles equipped with catalytic converters having been introduced in the mid 1970's.
Cordierite substrates, typically in the form of a honeycomb body, have long been preferred for use as substrates to support catalytically active components for catalytic converters on automobiles, in part due to cordierite ceramics' high thermal shock resistance. The thermal shock resistance is inversely proportional to the coefficient of thermal expansion. That is, honeycombs with a low thermal expansion have a good thermal shock resistance and can survive the wide temperature fluctuations that are encountered in the application. It is generally known that the coefficient of thermal expansion of cordierite bodies is about 18×10−7/° C. in the range of 25° C.-800° C. for those polycrystalline cordierite bodies in which the cordierite crystals are randomly oriented.
The production of cordierite (2MgO.2Al2O3.5SiO2) ceramics from mineral batches containing sources of magnesium, aluminum and silicon such as clay and talc is well known. Such a process is described in U.S. Pat. No. 2,684,919. U.S. Pat. No. 3,885,977 discloses the manufacture of thermal-shock-resistant cordierite honeycomb ceramics from clay/talc batches by extruding the batches and firing the extrudate to provide ceramics with very low expansion coefficients along at least one direction. Furthermore, this reference describes the principle of orienting the cordierite crystals with their crystallographic c-axis in the plane of the honeycomb webs, resulting in thermal expansion values as low as 5.5×10−7/° C.
Manufacturers work continuously to optimize the characteristics of cordierite honeycomb substrates to enhance their utility as catalyst carriers. Specifically, manufacturers continually strive to optimize the thermal shock resistance and strength of such cordierite honeycomb substrates. The following patents each relate to the manufacture of ceramic honeycombs exhibiting improved thermal shock resistance or coefficient of thermal expansion (CTE).
U.S. Pat. No. 4,434,117 (Inoguchi et al.) discloses the use of a raw material mixture comprising plate-shaped talc particles and non-plate shaped particles of other ceramic materials and thereafter anisostatically forming the mixed batch so as to impart a planar orientation to the plate-shaped talc particles and then drying and firing to obtain a formed ceramic body. The ceramic bodies formed in the Inoguchi reference exhibited thermal expansion coefficients as low as 7.0×10−7/° C.
U.S. Pat. No. 5,114,643 (Beall et al.) and U.S. Pat. No. 5,114,644 (Beall et al.) disclose methods of fabricating cordierite bodies involving selecting specific raw materials that will form the desired cordierite body. Specifically, these raw material selections should not include any clay or talc, should include a MgO-yielding component, and an Al2O3-yielding component having a particle size of no greater than 15 μm and 8 μm, respectively. The raw materials are mixed together, subsequently dried and fired for a time and a temperature sufficient to form the aforementioned cordierite body. The ceramic bodies formed by these Beall references exhibited thermal expansion coefficients of less than about 9×10−7/° C. from about 25 to about 1000° C.
While such ceramics represent an improvement in the thermal expansion coefficient properties over extruded cordierite ceramics produced using pre-existing processes, still further improvements in the coefficient of thermal expansion (CTE), particularly without measurable reduction in the ceramics' strength would be desirable. Strength has become an increasingly important consideration in the design of cordierite honeycomb substrates as a result of the move to producing thinner-walled, higher cell density, increased catalytic conversion efficiency and lower back pressure cordierite honeycomb catalyst carriers.
In addition to obtaining a low CTE, achieving good washcoatability for catalyst performance, as a virtue of relatively high total porosity and preferably desirable pore distribution, is also becoming an increasingly important consideration in the production of cordierite honeycomb substrates. To that end, further improvements in obtaining relatively high porosity cordierite substrates with desirable pore distribution while maintaining sufficient substrate strengths are also desirable.
It is therefore a principal objective of the present invention to provide an improved cordierite ceramic honeycomb article, and methods for manufacturing them, that exhibit adequate strength in combination with relatively high porosity, low thermal expansion, and preferably desirable pore distribution.